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1.
采用正交试验设计法,对正辛酸与硫酸镁反应形成有机硫化物的过程进行了模拟实验研究,探讨了反应温度、反应时间和反应体系中的含水量对有机硫化物形成的影响,结果表明,温度对有机硫化物生成的贡献率为59%,含水量的贡献率为26%,反应时间的贡献率为12%,反应温度是影响有机硫化物形成的关键因素.在优化有机硫化物形成条件之后,分别...  相似文献   

2.
酸性高锰酸盐指数的准确测定及影响因素探讨   总被引:2,自引:0,他引:2  
张云 《地下水》2010,32(1):111-112
采用酸性法对水质中高锰酸盐指数进行了测定,分析了影响其准确测定的因素,探讨了反应体系酸碱度、高锰酸钾标准溶液浓度、加热反应时间、滴定温度及滴定时间对酸性高锰酸盐指数准确测定的影响。实验表明:当反应体系的pH值小于2.0、高锰酸钾标准溶液浓度在0.0100mol/L左右、加热反应时间为30min、滴定温度保持在70℃~80℃、滴定操作时间控制在2min内时,酸性高锰酸盐指数测定的准确性较高。  相似文献   

3.
甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究   总被引:14,自引:4,他引:14  
碳酸盐岩地层中常伴有硫酸盐岩的沉积,在一定的温度和压力条件下,干酪根热降解生成的气态烃与硫酸盐岩接触后发生热化学还原反应(简称为TSR反应),使气态烃消失,这可能是造成生气死亡线的主要原因之一。本文对CH4-CaSO4热化学还原反应的热力学问题进行了探讨,发现该反应能够自发进行,而且升高温度对反应有利。利用高温高压模拟装置对CH4-CaSO4反应体系进行了初步的模拟实验研究,通过微库仑、气相色谱和傅里叶变换红外光谱(FT-IR)等分析手段对实验结果进行了进一步验证。结果表明,甲烷和固态硫酸钙能够发生热化学还原反应,生成硫化氢、碳酸钙和水。最后,将CH4-CaSO4反应体系同国内外的研究工作进行了对比,认为本实验研究能够更好地补充和完善TSR反应体系,解释地质条件下工业气藏的死亡线问题。  相似文献   

4.
丁康乐  王辉  罗跃  杨欢  虞启明 《沉积学报》2011,29(6):1180-1189
深埋碳酸盐岩储层中的水与金属氧化物可能会影响到吡咯类含氮化合物的保存。对吡咯—水—氧化铝反应体系进行了热模拟实验研究,根据模拟实验结果,探讨了反应机理,并考察了反应的动力学特征。结果表明,吡咯—水—氧化铝体系可以发生反应,产物主要为呋喃与氨气,升高温度对反应有利。氧化铝对有机氮与无机氧热化学交换作用起到了明显的催化作用...  相似文献   

5.
深层、超深层中有机酸的分布特征及其热稳定性对储层物性有着重要影响。采用高温高压水—岩模拟装置对储层中典型一元和二元有机酸(乙酸和乙二酸)的分解反应进行了模拟,对动力学参数进行了计算,并分析其影响因素。结果显示:乙二酸比乙酸更容易分解,且分解反应的速率更高;乙酸和乙二酸分解反应的起始温度分别为230 ℃和180 ℃,其反应速率随着温度的升高而急剧增加。反应体系中高pH值和钾长石的存在明显提高了乙酸和乙二酸分解反应的反应速率,但对起始温度影响较小。高流体压力和静岩压力均会抑制乙酸和乙二酸的分解,在提高有机酸分解反应起始温度的同时降低分解反应速率。从地质意义上来讲,相对高压、低地温的地层环境更有利于有机酸的保存,因此具有低地温梯度的沉积盆地形成深层—超深层优质储层的可能性更高。  相似文献   

6.
铁柱撑蒙脱石可见光催化降解活性艳橙性能及动力学研究   总被引:1,自引:0,他引:1  
采用铁柱撑蒙脱石(Fe-Mt)作为光催化剂,与H2O2在可见光条件下形成异相photo—Fenton(异相光芬顿)试剂对活性艳橙(X—GN)进行降解实验,研究不同反应体系对X—GN的降解情况,以及X—GN浓度、PH值、催化剂用量、H2O2浓度、反应温度等不同因素对X—GN光解过程的影响。结果表明:可见光照射下,在反应温度为30℃,pH为3.0,H2O2浓度为4.9mmol/L,Fe—Mt用量为0.6g/L,Fe-Mt/H2O2的可见光体系下,降解X—GN效果最好,140min后X—GN的降解率为98.5%;在此基础上进行的动力学研究则表明反应接近于表观一级反应。  相似文献   

7.
通过CaCl2添加剂对KAlSi3O8-CaSO4-CaCO3体系研究反应温度和反应时间的影响研究,结果表明:随着CaCl2加入量的增多,体系的反应温度下降,反应时间缩短,当CaCl2的加入量为10%时,反应温度可降至1000℃,反应时间降至25min,此时KAlSi3O8的转化率仍可高达83.24%。研究CaCl2的加入对KAlSi3O8-CaSO4-CaCO3反应体系动力学过程的影响,得出反应体系符合金斯特林格动力学方程:FK(G)=1-2/3G-(1-G)2/3=KKt,反应受扩散过程控制,计算出当CaCl2的加入量为10%时,体系的表观活化能可从原来的128.921kJ/mol下降至58.320kJ/mol。  相似文献   

8.
为了探究热活化过硫酸盐(PS)技术对水中氧氟沙星(OFX)的氧化降解作用,考察了反应温度、体系的初始pH、PS的初始浓度、OFX的初始浓度对OFX降解效果的影响;并在单因素实验的基础上,选取反应时间、体系的初始pH、PS的初始浓度和OFX的初始浓度4个因素进行了响应面优化实验。结果表明:最佳降解条件为,反应温度60℃、PS初始浓度4.0 mmol/L、pH=4.7、OFX初始浓度0.03 mmol/L、反应时间60 min,此时OFX的降解率为81.29%;4个因素对热活化PS降解OFX均有影响,其影响显著性从大到小为反应时间、OFX的初始浓度、PS的初始浓度、初始pH。利用响应曲面法模拟出反应体系的最佳条件,经实验验证,OFX降解率为93.78%,与预测最佳结果95.00%基本相符,表明模型可靠有效。  相似文献   

9.
以2-溴代异丁酸乙酯[2-(EiB)-Br]为引发剂,CuBr/2,2^1-bpy为催化体系,进行了甲基丙烯酸丁酯(BMA)在丙酮、丙酮/甲醇、丙酮/水中的原子转移自由基聚合,研究了溶剂、温度对聚合反应活性特征的影响.结果表明,水或甲醇的加入,使反应速率有所增加,水的影响最大;在其它反应条件相同时,水或甲醇对反应的影响在低温时更为明显.  相似文献   

10.
麻粒岩相岩石作为洞察下地壳的窗口一直备受重视。二十世纪九十年代以来麻粒岩研究的一个重要进展是利用变质相平衡的定量研究方法模拟岩石中所发生的深熔变质反应、熔体成分变化、及熔体丢失对变质矿物组合的影响等。本文利用KASH、NKASH和KFMASH等简单体系的相平衡关系,做出P-T投影图、组分共生图解和基于固定全岩成分的P-T视剖面图解,并结合有关实验岩石学结果,讨论了高温和超高温条件下变质泥质岩和杂砂岩中的变质熔融反应、矿物组合、全岩成分与P-T条件之间的相互关系。多数变质泥质岩和杂砂岩中饱和流体固相线熔融反应可利用NKASH体系中有水流体参与的熔融反应模拟,在没有外来流体注入时,这些反应可形成3mol%熔体。在不同体系中白云母脱水熔融反应型式及其P-T条件不同,如在NKASH和KFMASH体系中模拟计算的白云母脱水熔融反应与相应的实验结果相似,分别控制了白云母分解熔融的温度下限和上限;白云母的分解温度会随着其中Fe、Mg和Ti含量的增加而升高,也随着共生斜长石中钙长石组分增加而升高,泥质岩中白云母脱水熔融可以形成~10mol%熔体。在KFMASH体系中黑云母脱水熔融反应表现为4条单变反应,其理论计算的温度比实验模拟的结果低一些。在NCKFMASH体系或实际岩石中黑云母脱水熔融反应为滑动反应,如NCKFMASH体系中黑云母从其开始熔融到最后消失在泥质岩中可跨越~100℃,在杂砂岩中可跨越30~50℃。黑云母的稳定温度随着镁值升高而升高,其稳定上限受钛影响更大,黑云母脱水熔融可以形成超过30mol%~40mol%熔体。KFMASH体系中的相平衡模拟表明以出现斜方辉石+夕线石和假蓝宝石为特征的超高温组合易于出现于富镁泥质岩中,而对正常成分泥质岩在达到1000℃的超高温条件下,主要出现石榴石+夕线石(即夕线榴),该组合在更高温度反应形成假蓝宝石+尖晶石。利用饱和水固相线反应和白云母与黑云母分解反应可以更好地限定不同的变质相。如中压和低压条件下低角闪岩相和高角闪岩相的界限可利用NKASH体系中有水流体和白云母参与的熔融反应和亚固相线条件下的白云母分解反应限定;实验确定的泥质岩中黑云母开始熔融与消失的反应可分别用于限定高角闪岩相与(正常)麻粒岩相的界限,以及(正常)麻粒岩相和超高温麻粒岩相的界限。因此,从矿物组合角度,正常麻粒岩相可限定在黑云母开始熔融到完全消失的温度范围,超高温麻粒岩相可限定在黑云母消失(有石英存在)之后的温度范围。  相似文献   

11.
Hydrogen gas (H2) may be produced by the anoxic corrosion of steel components in underground structures, such as geological repositories for radioactive waste. In such environments, hydrogen was shown to serve as an electron donor for autotrophic bacteria. High gas overpressures are to be avoided in radioactive waste repositories and, thus, microbial consumption of H2 is generally viewed as beneficial. However, to fully consider this biological process in models of repository evolution over time, it is crucial to determine the in situ rates of microbial hydrogen oxidation and sulfate reduction. These rates were estimated through two distinct in situ experiments, using several measurement and calculation methods. Volumetric consumption rates were calculated to be between 1.13 and 1.93 μmol cm−3 day−1 for H2, and 0.14 and 0.20 μmol cm−3 day−1 for sulfate. Based on the stoichiometry of the reaction, there is an excess of H2 consumed, suggesting that it serves as an electron donor to reduce electron acceptors other than sulfate, and/or that some H2 is lost via diffusion. These rate estimates are critical to evaluate whether biological H2 consumption can negate H2 production in repositories, and to determine whether sulfate reduction can consume sulfate faster than it is replenished by diffusion, which could lead to methanogenic conditions.  相似文献   

12.
TSR(硫酸盐热化学还原反应)是高含硫化氢天然气形成的重要途径,是指烃类在高温条件下将硫酸盐还原生成H2S、CO2等酸性气体的过程。由于硫化氢的剧毒和强腐蚀性,在石油天然气行业的钻井、完井、修井、净化加工以及运输等各个方面的危害一直备受人们的关注,对硫化氢和TSR的评价一直是负面的,在油气勘探中更多是在回避。最近研究发现,TSR作用对石油天然气工业具有重要的积极作用。TSR的发生,首先需要硫酸盐类溶解提供SO42-,储集空间得到初步改善;其次TSR反应形成的硫化氢,溶于水后显示出较强的酸性溶蚀作用,对白云岩储层具有最佳的溶蚀效果。在高温条件和储层中地层水的作用下,硫化氢与白云岩发生较强烈的酸性流体-岩石相互作用(水岩反应),促进了白云岩次生孔洞的发育和高孔高渗优质储集层的形成,使油气储层保存下限增大和深部天然气聚集成藏成为可能。而目前飞仙关组高含硫化氢气藏普遍压力系数小、充满度低,这与TSR及硫化氢对储层溶蚀导致储集空间增容有关。四川盆地油气勘探结果证实,所有高含硫化氢天然气藏均对应了次生孔隙十分发育的优质储层,岩性主要以白云岩为主,储层埋藏深度超过8 000 m时依然发育优质储层。  相似文献   

13.
Natural gas from the Zhaolanzhuang field of the Jizhong Superdepression, Bohai Bay Basin contains the highest proportions of H2S (40–92%) among the sour gases encountered in China. The gas payzones include the Eocene–Oligocene Kongdian Formation (Ek) and the Es4 member of the Shahejie Formation. The sedimentary sequence consists of halite, anhydrite, carbonate, sandstone and shale interbeds deposited in the evaporative brackish water lacustrine – salt lake setting. In the deepest part of the Jinxian sag, the total thickness of evaporites is more than 1000 m, of which halite accounts for over 40%. Various organic-rich mudstones intercalated with the evaporites are currently within the conventional hydrocarbon window (with a depth of 2500–3500 m), and likely the source for the oil and sour gas in the Zhaolanzhuang field. The temperatures of the gas reservoirs range from 75 to 100 °C, too low for significant thermochemical sulfate reduction. The co-occurrence of abundant elemental sulfur with the sour gas and the δ34S values of the various sulfur-containing compounds indicate that the H2S gases were most likely derived from much deeper source kitchens where significant thermochemical sulfate reduction has occurred.  相似文献   

14.
The effect of dissolved sulfate concentration on the rate of bacterial sulfate reduction in marine sediment from Long Island Sound was examined using a radio-sulfur technique. The experimental results show that the rate is independent of the dissolved sulfate concentration until low levels are reached (<3 mM), and that, when interpreted using a Monod-type rate law, a saturation constant, Ks, of 1.62 ± 0.16 M results. This weak dependence implies that the dissolved sulfate exerts only a limited influence on the rate of sulfate reduction in marine sediments. Given such a weak dependence, dissolved sulfate profiles in marine sediments must resemble profiles generated by models with sulfate independent kinetics. Initially, this would suggest that currently used sulfate-independent diagenetic models are appropriate in modelling sulfate profiles. However, comparison of these models with those containing weak sulfate-dependent kinetic terms shows that there exists considerable disagreement between these models when the parameter grouping (Dsk)12/w is larger than ~0.2 and smaller than ~3.0. (Here Ds is the SO;4 diffusion coefficient, k the organic matter decay constant and w the sediment burial velocity.) When the currently used models are corrected by employing physically meaningful boundary conditions, this divergence disappears. The modelling results, therefore, confirm the conclusion that any sulfate dependence inherent to the reduction kinetics does not appreciably affect sulfate pore water profiles, and that previous diagenetic studies using strong sulfate dependent models are erroneous.  相似文献   

15.
Goethite-enhanced anaerobic bio-decomposition of sulfate minerals   总被引:1,自引:0,他引:1  
The effects of goethite on the anaerobic bio-decomposition of sulfate minerals were investigated by using the beef extract as a carbon source and the activated sludge as the source of mixed bacteria. Solution pH, sulfate concentration, total iron ion concentration and the solid products of four different batch tests were monitored and analyzed. Experimental results showed that the presence of iron oxide can improve the alkalinity of the reaction system which results in the increase of pH value. Moreover, the added goethite consumed a large amount of H2S generated from the sulfate minerals by SRB, thereby significantly enhancing the decomposition of gypsum and anhydrite compared with the control batch tests. In addition, the SEM observation and the EDS spectra showed that there were some rod-shaped microorganisms and new generated minerals, such as iron sulfide, calcium carbonate crystals, and elemental sulfur. Both of the proliferation of new minerals (iron sulfide and calcium carbonate crystals) and the complete disappearance of sulfate minerals indicated that iron oxide can play the role in fixing the S element through the metabolism of SRB and hence improve the bio-decomposition of sulfate minerals.  相似文献   

16.
The anaerobic oxidation of methane in aquatic environments is a globally significant sink for a potent greenhouse gas. Significant gaps remain in our understanding of the anaerobic oxidation of methane because data describing the distribution and abundance of putative anaerobic methanotrophs in relation to rates and patterns of anaerobic oxidation of methane activity are rare. An integrated biogeochemical, molecular ecological and organic geochemical approach was used to elucidate interactions between the anaerobic oxidation of methane, methanogenesis, and sulfate reduction in sediments from two cold seep habitats (one brine site, the other a gas hydrate site) along the continental slope in the Northern Gulf of Mexico. The results indicate decoupling of sulfate reduction from anaerobic oxidation of methane and the contemporaneous occurrence of methane production and consumption at both sites. Phylogenetic and organic geochemical evidence indicate that microbial groups previously suggested to be involved in anaerobic oxidation of methane coupled to sulfate reduction were present and active. The distribution and isotopic composition of lipid biomarkers correlated with microbial distributions, although concrete assignment of microbial function based on biomarker profiles was complicated given the observed overlap of competing microbial processes. Contemporaneous activity of anaerobic oxidation of methane and bicarbonate-based methanogenesis, the distribution of methane-oxidizing microorganisms, and lipid biomarker data suggest that the same microorganisms may be involved in both processes.  相似文献   

17.
硫酸盐热化学还原作用的启动机制研究   总被引:1,自引:0,他引:1  
硫酸盐热化学还原作用(TSR)是导致高含硫化氢天然气生成和聚集、碳酸岩盐储层酸化和溶蚀的重要因素,是地质盆地内烃-水-岩三者之间的复杂反应。本文利用黄金管热模拟实验,对TSR反应的可能启动机制及控制因素进行了研究。通过不同盐溶液与原油的热解实验,证实了硫酸盐的存在是启动TSR反应的必要因素,MgSO4比CaSO4和Na2SO4更容易启动TSR反应,体系中盐度的增加会加速H2S的生成。实验结果表明,不同水介质条件下,TSR反应的程度与溶液的离子强度呈正相关,弱酸性环境并不足以启动TSR反应;原油中不稳定含硫化合物的含量越高越有利于TSR反应的发生,饱和链烷烃比原油中其它组分更容易引发TSR反应,且大分子烷烃比小分子烷烃更容易被硫酸盐氧化。  相似文献   

18.
张水昌  朱光有  何坤 《岩石学报》2011,27(3):809-826
硫酸盐热化学还原作用(Thermochemical sulfate reduction, TSR)是发生在油气藏中复杂的有机-无机相互作用,它不仅会引起含H2S天然气的富集,其产生的酸性气体对碳酸盐岩储层还具有明显的溶蚀改造作用。本文基于黄金管热模拟实验,研究了TSR反应对原油裂解气的生成的影响,发现这种氧化还原反应的存在能明显降低原油的稳定性,促进具高干燥系数的含H2S天然气的生成。结合原位激光拉曼实验结果,证实了实际油藏中启动TSR反应的最可行的氧化剂应该是硫酸盐接触离子对(CIP)。全面探讨了影响TSR反应的地质和地球化学因素,提出除了初始原油的组分特征、不稳定含硫化合物(LSC)的含量外,地层水的含盐类型及盐度同样是控制TSR反应的关键因素。同时,基于大量地质分析,发现TSR对碳酸盐岩储层具有明显的溶蚀改造作用。结合溶蚀模拟实验,提出了酸性流体对碳酸盐储层溶蚀改造的机制,且深层碳酸盐岩层存在一个由TSR作用形成的次生孔隙发育带。研究认为,烃类与硫酸盐矿物的氧化还原反应与其产物对碳酸盐岩储层的改造是TSR作用的两个不可分割的部分,它们相互依存和制约。  相似文献   

19.
The mode of incorporation of sulfate ion in travertine was discussed on the basis of chemical compositions, i.r. and laser Raman spectra. These data strongly suggest that most of the sulfate ions in the calcitic travertine replace carbonate ions. This conclusion is in good harmony with the facts that calcite incorporates more sulfate ions than aragonite does and that the sulfate content of manganoan calcite decreases with increasing manganese content (Takano et al. 1977). Based on this conclusion, retarding effect of sulfate ion on the precipitation of calcite from solution was discussed.  相似文献   

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